JP7321387B2 - resin composition - Google Patents

Description

The present invention is a resin composition comprising a polyarylene sulfide resin, spherical graphite, a fibrous filler, and a fluororesin, which maintains excellent strength and does not cause fusion during frictional wear between the same materials, The present invention also relates to a resin composition having excellent abrasion resistance.

Polyarylene sulfide resins are engineering plastics that are excellent in chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used in applications such as electrics and electronics, vehicles, aircraft, and housing equipment as metal substitute materials by taking advantage of their excellent properties. Especially recently, application to sliding parts such as gears and bearings has been studied. As a technique for improving the slidability of polyarylene sulfide resin, a method of filling tetrafluoroethylene resin into polyarylene sulfide is known (Patent Document 1). However, in the case of parts such as gears in which resins slide against each other, there is a problem that heat generated when the same materials wear against each other leads to fusion. For this reason, it has been common to combine different resins to form a gear. As an attempt to suppress the heat generation of polyarylene sulfide, for example, a resin composition in which polyarylene sulfide is blended with an amorphous thermoplastic resin, flake graphite, and a fibrous filler has been proposed (Patent Document 2). However, when flake graphite is used, although the heat dissipation property of the resin is improved, the abrasion resistance of the resin is not sufficient. Also, a resin composition (Patent Document 3) composed of polyarylene sulfide resin, aromatic polyamideimide, graphite, carbon fiber and solid lubricant has been proposed as a bearing part for motors. Nothing was said about wearability.

JP-A-63-213561 Japanese Patent Application Laid-Open No. 2003-268236 JP 2010-281348 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition that maintains excellent strength, does not fuse when the same materials are worn by friction, and has excellent wear resistance.

As a result of extensive studies, the inventors of the present invention have found that a resin composition composed of polyarylene sulfide resin, spherical graphite, fibrous filler, and fluororesin maintains excellent strength and is fused during friction wear between the same materials. The present inventors have found that a resin composition that does not cause the occurrence of abrasion and has excellent wear resistance has led to the present invention.
That is, according to the present invention, the objects of the invention are achieved by the following.

1. (A) polyarylene sulfide resin (component A) 100 parts by weight, (B) spherical graphite (component B) 5 to 150 parts by weight, (C) fibrous filler (component C) 5 to 150 parts by weight and ( D) A resin composition containing 5 to 100 parts by weight of a fluororesin (component D).

2. 1. The resin composition according to item 1 above, which contains 5 to 100 parts by weight of (E) a non-fibrous filler (component E) per 100 parts by weight of component A.

3. 3. The resin composition according to item 1 or 2, wherein the particle size of component B is 10 μm to 35 μm.

4. 4. The resin composition according to any one of the preceding items 1 to 3, wherein the C component is glass fiber.

5. A molded article comprising the resin composition according to any one of 1 to 4 above.

6. A) Per 100 parts by weight of polyarylene sulfide resin (component A), (B) 5 to 150 parts by weight of spherical graphite (component B), (C) fibrous filler (component C) 5 to 150 parts by weight and (D ) A method for producing a resin composition according to the preceding item 1, which comprises mixing 5 to 100 parts by weight of a fluororesin (component D).

INDUSTRIAL APPLICABILITY The resin composition of the present invention maintains excellent strength, does not fuse when the same materials are worn, and has excellent wear resistance. is.

The details of the present invention will be described below.

(A component: polyarylene sulfide resin)
As the polyarylene sulfide resin used as component A in the present invention, any resin may be used as long as it belongs to the category called polyarylene sulfide resin.

Examples of polyarylene sulfide resins include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and diphenylene sulfide units. , substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units Preferred, and more preferred is poly(p-phenylene sulfide).

The polyarylene sulfide resin used as the A component of the present invention preferably has a dispersity (Mw/Mn) represented by a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 2.7 or more, more preferably 2. 0.8 or more, more preferably 2.9 or more. If the degree of dispersion is less than 2.7, burrs may occur more frequently during molding. Although the upper limit of the degree of dispersion (Mw/Mn) is not particularly defined, it is preferably 10 or less. Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). 1-Chloronaphthalene was used as a solvent, and the column temperature was 210°C.

A method for producing the polyarylene sulfide resin is not particularly limited, and polymerization is performed by a known method. For example, the production methods described in US Patent Nos. 4,746,758, 4,786,713, JP-T-2013-522385, JP-A-2012-233210 and JP-A-5167276 can be mentioned. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

The manufacturing method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to give a diiodoaryl compound. In the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a polymerization terminator to prepare a polyarylene sulfide resin. Iodine is generated in gaseous form in this process, and this is recovered and used again in the iodination process. Iodine is essentially a catalyst.

A representative solid sulfur used in the method of preparation includes the cyclooctasulphur form (S ₈ ) with 8 atoms linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited and may be used in any form as long as it is solid or liquid at room temperature.

Typical diiodoaryl compounds used in the production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl Derivatives of iodoaryl compounds to which a group or sulfone group is attached, or to which oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodine. It is a compound in which iodine is symmetrically positioned at both ends of an aryl compound, such as biphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

Typical polymerization terminator used in the production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of benzothiazolesulfenamides include N-cyclohexylbenzothiazole 2-sulfenamide, N,N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, and benzothiazolesulfenamide. , dibenzothiazole disulfide, and N-dicyclohexylbenzothiazole 2-sulfenamide. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of aromatic sulfide compounds include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. In any polymerization terminator, one or more functional groups may be substituted on the conjugated aromatic ring skeleton. Examples of the functional group include a hydroxy group, a carboxy group, a mercapto group, an amino group, a cyano group, a sulfo group, a nitro group, etc. Preferred examples include a carboxy group and an amino group, and more preferred examples include includes a carboxy group and an amino group showing a peak at 1600 to 1800 cm ^-1 or 3300 to 3500 cm ^-1 on the FT-IR spectrum. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

A polymerization reaction catalyst may be used in the production method, and a typical polymerization reaction catalyst is a nitrobenzene-based catalyst. Preferred examples of nitrobenzene catalysts include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, 2,6-diiodo-4- At least one selected from the group consisting of nitroamines can be mentioned. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

By using this polymerization method, it is possible to obtain a polyphenylene sulfide resin excellent in cost performance without substantially reducing the chlorine content and sodium content.

The polyphenylene sulfide resin of the present invention may also contain polyphenylene sulfide resins obtained by other polymerization methods.

(B component: spherical graphite)
In the present invention, the spherical graphite may have an aspect ratio (major axis/minor axis) of 2.0 or less. The aspect ratio is, for example, the ratio of the length of the longest portion to the length of the shortest portion (most length of the longest part/length of the shortest part).

The spherical graphite used in the present invention is not particularly limited as long as the graphite has a spherical shape. If the shape of the graphite is not spherical, the abrasion resistance is poor.

The particle size of graphite is preferably 10 to 35 μm, more preferably 15 to 30 μm, still more preferably 15 to 20 μm. If the particle size of the B component is less than 10 µm, fusion between the same materials may occur, and if it exceeds 35 µm, the graphite tends to fall off, and the abrasion resistance may decrease.

Examples of such spherical graphite are commercially available as S-10, S-15, and S-20 from Nishimura Graphite Co., Ltd., and as SG-BH and SG-BL30 from Ito Graphite Industry Co., Ltd. Available.

The content of component B is 5 to 150 parts by weight, preferably 15 to 130 parts by weight, more preferably 20 to 100 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 5 parts by weight, sufficient heat dissipation cannot be obtained, and fusion occurs due to frictional heat between the same materials. On the other hand, if it exceeds 150 parts by weight, productivity or molding processability will be lowered, and in the worst case, extrusion molding will not be possible.

(C component: fibrous filler)
The inorganic fiber filler used in the present invention is not particularly limited as long as it is a fibrous filler. Examples include glass fiber, carbon fiber, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, and inorganic filler coated with a conductive substance. Fiber, aramid fiber and carbon fiber are more preferred. In addition, pretreatment of these fibrous fillers with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound leads to better mechanical strength. is preferable in the sense of obtaining

The fiber thickness of the fibrous filler is preferably 3-30 μm, more preferably 4-20 μm.

Specific examples of conductive substances in inorganic fillers coated with conductive substances include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped), and In ₂ O ₃ (antimony-doped). Examples of the inorganic filler to be coated include glass fiber and carbon fiber. Examples of coating methods include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. Moreover, these may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

The content of component C is 5 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 20 to 130 parts by weight, per 100 parts by weight of component A. If the content of the C component is less than 5 parts by weight, a sufficient reinforcing effect cannot be obtained, and if it exceeds 150 parts by weight, the productivity or molding processability will decrease, and in the worst case, extrusion molding will not be possible.

(Component D: fluorine resin)
The fluororesin used as the component D of the present invention is preferably a polymer having a carbon chain in the main chain and a fluorine atom bond in the side chain, or a copolymer having such a polymer. . Specific examples include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-fluoroalkyl vinyl ether- Examples include fluoroolefin copolymers and ethylene-trichlorofluoroethylene copolymers. Among them, polytetrafluoroethylene is preferable, and both calcined and uncalcined polytetrafluoroethylene can be used. A powdery product obtained by subjecting the polytetrafluoroethylene to sintering treatment temperature of 360° C. or higher is particularly preferable. Polytetrafluoroethylene preferably has a melting point of 320 to 335° C., more preferably 325 to 330° C., as measured by the DSC method in order to prevent reaggregation. The average particle size of polytetrafluoroethylene is preferably 0.1 to 100 μm, more preferably 1 μm to 20 μm, as determined by a method of measuring a dispersion in perchlorethylene by a light transmission method. The average particle size referred to here is the weight average particle size measured using the laser diffraction/scattering method (MICOTRAC method). The polytetrafluoroethylene preferably has a number average molecular weight of 100,000 or more, more preferably 200,000 or more.

Examples of such polytetrafluoroethylene include KT-600M, KTL-620, and KTL-450A from Kitamura Co., Ltd.; Lebron L-5 and L-2 from Daikin Industries, Ltd.; They are commercially available as L150J, L169J, L170J, and L172J from Ifluoropolymers Co., Ltd., and Teflon (registered trademark) TLP-10F-1 from DuPont-Mitsui Fluorochemicals Co., Ltd., and are readily available.

The content of component D is 5 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of component A. If the content is less than 5 parts by weight, sufficient abrasion resistance cannot be obtained, and if it exceeds 100 parts by weight, strand breakage or surging will occur during kneading.

(E component: non-fibrous filler)
The resin composition in the present invention can be used in combination with a non-fibrous filler as long as the effects of the present invention are not impaired. Non-fibrous fillers are not particularly limited, but sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swelling layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide. , magnesium oxide, zirconium oxide, titanium oxide, iron oxide and other metal compounds, calcium carbonate, magnesium carbonate, carbonates such as dolomite, calcium sulfate, barium sulfate and other sulfates, glass beads, ceramic beads, boron nitride , silicon carbide, calcium phosphate and silica.

The content of component E is preferably 5 to 100 parts by weight, more preferably 5 to 80 parts by weight, still more preferably 10 to 50 parts by weight, per 100 parts by weight of component A. If the content of component E is less than 5 parts by weight, a sufficient reinforcing effect may not be obtained, and if it exceeds 100 parts by weight, productivity or molding processability may decrease, and in the worst case, extrusion molding may not be possible. be.

The resin composition in the present invention can contain an elastomer component within a range that does not impair the effects of the present invention. Suitable elastomer components include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and core-shell of silicone-acrylic composite rubber graft copolymer. Examples thereof include graft copolymer resins, thermoplastic elastomers such as silicone thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers.

The resin composition in the present invention can contain other thermoplastic resins as long as the effects of the present invention are not impaired. Other thermoplastic resins include, for example, polyethylene resins, polypropylene resins, general-purpose plastics represented by polyalkyl methacrylate resins, polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystalline polyester resins, polyamide resins, cyclic Engineering plastics represented by polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), etc., so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone can be mentioned.

The resin composition of the present invention contains antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites, and substituted compounds thereof), weathering agents (resorcinols, Salicylates, benzotriazoles, benzophenones, hindered amines, etc.), release agents and lubricants (montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc.) , pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.) ), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc. ), flame retardants (red phosphorus, phosphates, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin Alternatively, a combination of these brominated flame retardants and antimony trioxide, etc.) and other polymers can be added.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading rolls, and extruder. Melt-kneading by a twin-screw extruder is preferable, and if necessary, it is preferable to feed optional components into other melt-mixed components from the second supply port using a side feeder or the like.

The resin extruded as described above is either directly cut into pellets, or formed into strands and then cut into pellets by a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization. The shape of the obtained pellets can take general shapes such as cylindrical, prismatic, and spherical shapes, and is more preferably cylindrical. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.5 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-4 mm.

(About molded products)
A molded article using the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, heat insulation metal Mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, ultra-high speed injection molding, and the like can be mentioned. For molding, either a cold runner method or a hot runner method can be selected. Extrusion molding can also be used to obtain various shaped extruded products, sheets, films, and the like. Inflation method, calendering method, casting method and the like can be used for forming sheets and films. Furthermore, it can be molded as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

The best mode of the present invention, which the present inventors consider to be the best, summarizes the preferable range of each of the requirements described above, and representative examples thereof are described in the following examples, for example. Of course, the present invention is not limited to these forms.

[Evaluation of Resin Composition]
(1) Tensile strength at break Measured according to ISO527 (measurement conditions: 23°C). In addition, the test piece was molded by the following method. It means that the larger the numerical value, the better the mechanical strength of the resin composition.

(2) Specific Wear Amount A ring-on-ring friction wear test was performed using a friction wear tester (EFM-III-EN manufactured by A&D Co., Ltd.). According to JISK7218, a hollow cylindrical test piece having an outer diameter of 25.6 mm, an inner diameter of 20 mm and a length of 15 mm was used. Identical test pieces were fixed to a friction wear tester, and the lower test piece was rotated at a speed of 500 mm/s under a load of 50 N for 100 minutes. From the results, the specific wear amount was calculated by the following formula. A smaller value means better wear resistance. In addition, when the load became unstable due to fusion between the test pieces during the test, it was evaluated as "x". In addition, the test piece was molded by the following method in the same manner as in (1).
Specific wear amount = (M1-M2) / (ρ x W x L)
M1: Average value of the weights of the upper and lower test pieces before the test (mg)
M2: average value of the weights of the upper and lower test pieces after the test (mg)
ρ: resin density W (load): 50N
L (mileage): 3000m

[Examples 1 to 10, Comparative Examples 1 to 11]
Polyarylene sulfide resin, spherical graphite, fibrous filler, and fluororesin were melt-kneaded using a vented twin-screw extruder in the amounts shown in Table 1 to obtain pellets. The vented twin-screw extruder used was TEX30α-38 (completely meshed, co-rotating) manufactured by Japan Steel Works, Ltd. The extrusion conditions were a discharge rate of 20 kg/h, a screw rotation speed of 200 rpm, and a vent vacuum degree of 3 kPa. The fibrous filler and spherical graphite excluding aramid fiber are supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin, aramid fiber and fluororesin are supplied from the first supply port to the extruder. supplied. The first feed port here is the feed port farthest from the die, and the second feed port is the feed port located between the die and the first feed port of the extruder. After drying the obtained pellets at 130 ° C. for 6 hours with a hot air circulation dryer, an injection molding machine (manufactured by Toshiba Machine Co., Ltd. EC160NII-4Y) was used for evaluation at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. A test piece was molded.

Each component of symbol notation in Table 1 is as follows.
<A component>
A-1: Polyphenylene sulfide resin obtained by the following production method [manufacturing method]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide as a polymerization terminator (content of 0.65% by weight based on the weight of the final polymerized PPS) was added and heated to 180°C. After heating to completely melt and mix them, the temperature was raised to 220°C and the pressure was lowered to 200 Torr. The resulting mixture was polymerized for 8 hours while changing the temperature and pressure stepwise so that the final temperature and pressure were 320° C. and 1 Torr, respectively, to prepare a polyphenylene sulfide resin. The dispersity (Mw/Mn) represented by weight average molecular weight (Mw) and number average molecular weight (Mn) was 4.3.

<B component>
B-1: S-20 (Nishimura Graphite Co., Ltd. spherical graphite particle size: 20 μm)
B-2: 10099M (Nishimura Graphite Co., Ltd. Scale graphite particle size: 57 μm)
B-3: AG-20 (manufactured by Teijin Limited, artificial graphite (amorphous), particle size: 20 μm)

<C component>
C-1: Circular cross-section chopped glass fiber (T-732H manufactured by Nippon Electric Glass Co., Ltd., diameter: 10.5 μm, cut length: 3 mm, urethane/epoxy sizing agent)
C-2: Carbon fiber (IMC702 6 mm manufactured by Toho Tenax Co., Ltd. Long diameter: 6 μm, cut length: 6 mm, tensile modulus: 282 GPa, tensile strength: 5,490 MPa, urethane-based sizing agent)
C-3: Wholly aromatic polyamide fiber (manufactured by Teijin Limited: para-aramid fiber T322EH major diameter 12 μm, cut length 3 mm, polyester sizing agent)

<D component>
D-1: Polytetrafluoroethylene (Kitamura Co., Ltd. KT-600M firing type melting point 328 ° C.)
<E component>
E-1: Calcium carbonate (KSS-1000 manufactured by Calfine Co., Ltd.)

Claims (5)

(A) polyarylene sulfide resin (component A) 100 parts by weight, (B) spherical graphite (component B) 5 to 150 parts by weight, (C) fibrous filler (component C) 5 to 40 parts by weight and ( D) A resin composition containing 5 to 100 parts by weight of a fluororesin (component D) and a glass fiber as the component C. The resin composition according to claim 1, which contains 5 to 100 parts by weight of (E) a non-fibrous filler (component E) per 100 parts by weight of component A. 3. The resin composition according to claim 1, wherein the particle size of component B is 10 μm to 35 μm. A molded article made of the resin composition according to any one of claims 1 to 3 . A) Per 100 parts by weight of polyarylene sulfide resin (Component A), (B) 5 to 150 parts by weight of spherical graphite (Component B), (C) 5 to 40 parts by weight of a fibrous filler that is glass fiber (Component C) and (D) 5 to 100 parts by weight of a fluororesin (component D).